JPS6115068B2 - - Google Patents

Description

[Detailed Description of the Invention] The present invention is based on the following formula () The compound represented by is esterified to form the following formula () This relates to an improved method for producing the compound shown in
92 to 100, which is 1 to 2.5 times the molar amount of SO ₃
% sulfuric acid or sulfur trioxide or sulfuric acid containing sulfur trioxide in a machine operating with a summing action.

In the above formulas () and (), the β-hydroxyethylsulfonyl group or β-sulfatoethylsulfonyl group is present at the 3'- or 4'-position of the anilide group, and the amino group is at the 3'- or 4'-position of the benzoyl group. -or 4-
It exists in the position.

The preparation of 4-amino-3'-(β-sulfatoethylsulfonyl)-benzanilide by the process of the invention is particularly advantageous.

Compounds of formula () are suitable as initial products (diazo component) for producing azo dyes.

Methods for converting a compound of formula () into a compound of formula () are known per se. However, the previously reported methods require a large excess of sulfuric acid, which requires the formula ()
The esterification product must be diluted with water, neutralized and separated during work-up and isolation or further processing to give the dye. This is generally done by forming a sparingly soluble diazonium salt of a compound of the formula () which precipitates when the sulfuric acid solution is diluted with ice and water after the esterification, which is carried out simultaneously with the diazotization using nitrosylsulfuric acid. Make sure to suck up the -. Strongly acidic mother liquors must be neutralized before being flushed down the drain. Recovery of sulfuric acid is therefore practically impossible. Moreover, this acid contaminates wastewater in its pure form or in neutralized form as soluble sulfate.

The known esterification process also has the disadvantage that the compound of formula () is obtained as a solution in sulfuric acid. This solution is hardly suitable for storage, for example for subsequent processing.

Esterification of compounds of the formula () is carried out, for example, according to German Patent No. 1126547 in Examples 1 and 2.
In this case, 15 times the molar amount of concentrated sulfuric acid is used. Examples 1 and 2 of German Patent Application No. 1206107 and German Patent Application No. 1206108
The procedure is similar in Examples 1 and 2 of the specification.

Further, from Example 3 of DE 14 43 877, the compound of formula () is converted into the corresponding sulfuric acid half ester of formula () using 3 times equimolar amount of amidosulfonic acid in pyridine. It is well known that it can be used. Although this means that the amount of esterifying agent conventionally used in excess can be significantly reduced, the pyridine used must then be sufficiently distilled off under reduced pressure. Nevertheless, approximately 1/4 of the pyridine used in this case still enters the mother liquor when the sulfuric acid half ester is further processed to give the dye. Therefore, the pyridine must be removed from the mother liquor in some way before this wastewater reaches the drain.

There was therefore an urgent need for an esterification process which was free from such drawbacks and which was practically completely or only slightly environmentally polluting.

Thus, the present inventor has the above formula ()
3'- or 4'-(β-hydroxy-ethylsulfonyl)-3- or -4-amino-benzanilide-
Esterify the compound as shown below to obtain the formula ()
We have found an improved method of making the corresponding sulfuric acid half ester shown by This method is characterized by using 92 to 100% sulfuric acid, sulfur trioxide, or sulfur trioxide-containing sulfuric acid, preferably trioxide, in an equimolar amount of 1 to 2.5 times the molar amount of the compound of formula () and _SO3 . about 70 sulfur
% by weight, in particular from 15 to 65% by weight, in a machine operating with a summing effect.

Machines which operate with a mixing action should be understood to be suitable for mixing, dispersing or homogenizing, and which are capable of mixing liquid and solid components with each other under the action of strong forces. In this case, this mixing is usually carried out under high pressure in the following manner. i.e. mechanical parts, such as rolls, disks, etc., moving in parallel or oppositely and expediently running with different speeds.
Rollers, closely intertwined gears and worms are used to mix the components together under high pressure and optionally under the application of shearing forces. 〓
A machine that has a sum function (hereinafter referred to as a sum machine)
Examples include, in addition to the actual mills and extruders themselves, eg saw blade dissolvers, rotor-stator mills, dispergators and roller mills. These machines can operate either discontinuously or continuously and are known in large numbers commercially. Discontinuously operating wafers include, for example, double tank type wafers, sigma-paddle type wafers, dispersion wafers, Banbury dispersion mixers, etc., while continuously operating wafers include For example:
Japanese extruders (also known as Ulmanns)
Encylopa¨die der Technischen Chemie, Vol.1
(1951), p.725-727; Ullmanns Encyclopaedia
der Technischen Chemie, 4, Edition, Vol.2
(1972), p. 23, 292-299. ].

The process can be carried out either by first charging one of the reaction components into a machine operating with a summation action and then adding the second component thereto, or alternatively by introducing both components simultaneously or in a mixture into a machine. It is easy to implement.

The sulfuric acid used in this reaction is concentrated sulfuric acid (96%)
Preference is given to using it as a so-called monohydrate (100% sulfuric acid) or as fuming sulfuric acid. Furthermore, in order to esterify the compound represented by the formula (), an equimolar amount of 1 to 2.2 times, particularly preferably 1.0 to 1.5 times, especially 1.1 to 1.5 times the molar amount of SO ₃ is used. Preference is given to using esterifying agents.

The reaction temperature can be from 10°C to 130°C, preferably the reaction is carried out using sulfuric acid or oleum or sulfur trioxide in a simmering machine at a temperature of from 70°C to 110°C. Temperature control is usually achieved by means of a cooling jacket or a heating jacket on the machine. The processing time of the reaction mixture in the mixing machine depends on the temperature, the mixing strength, and the esterifying agent used.
It takes a few minutes to a few hours. Conveniently 70-110℃
operating at a temperature of from 5 minutes to 6 hours, with a reaction time of between 5 minutes and 6 hours, this time being particularly applicable in such conditions. Depends on - depends on.

During the merging process, inert additives are added, such as diatomaceous earth, to improve the merging action or the heat transfer of the merging mixture.
Talc or metal powders can also be added together, and these additives can be added to the sulfuric acid half ester of formula () prepared or the dye prepared therefrom to its aqueous solution during post-treatment or further processing of the hydrate. can be separated again by simple filtration.

The work-up of the reaction product after esterification in the machine is carried out in the customary manner customary to those skilled in the art. This work-up is advantageously carried out in such a way that the reaction product is dissolved in water and the solution is neutralized at the same time. This neutralization is preferably carried out using sodium bicarbonate or sodium carbonate. The neutral or completely slightly acidic solution is then evaporated to dryness or spray-dried, optionally after the above-mentioned inert additives have been separated off, for example by filtration or centrifugation. In this way, for example, upon neutralization with the abovementioned sodium salts, a compound of formula () is obtained in the form of its sodium salt. Potassium bicarbonate or potassium carbonate can likewise be used for neutralization. Another possibility for working up the hydrate is to dissolve the hydrate in water and then neutralize it with calcium carbonate, sucking off the formed and precipitated calcium sulfate, and
Sodium oxalate or oxalic acid and sodium carbonate or sodium bicarbonate are added to the solution and the solution is separated from the precipitate formed in a conventional manner, for example by filtration or centrifugation, and then spray-dried. In the case of this new esterification process, the amount of gypsum formed is significantly lower than in the previously known processes.

However, the outstanding and important advantage of the esterification process according to the invention is that no further treatment of the final product is necessary. That is, the reaction product is obtained from the washing machine as a powder, or as brittle or small lumps, or as a plastic material. And the products can be easily stored and transported in these forms. The product can be used for easy wastewater-free and environmentally satisfactory further processing, i.e. the following formula () It is possible to produce fiber-reactive azo dyes shown in

In the above formula, the β-sulfatoethylsulfonyl group is present at the 3'- or -4'-position of the anilide group, and the azo group is present at the 3- or 4-position of the benzoyl group of the diazo component.
K is a residue of a coupling component and can also contain an azo group. The product of formula () obtained by the esterification method according to the present invention is 95
A degree of esterification of ~100% and a high yield are obtained and, surprisingly, in a higher quality than with known processes. The dyes obtained from the products of the esterification process according to the invention are therefore of outstanding quality and exhibit a high degree of purity of color in the dyeings and prints on cellulose fiber materials produced with them; It can also be obtained in high yield calculated from the starting compound of formula () above.

When 1 to 2 moles of the esterifying agent are used per mole of the compound of formula (), the hydrate is usually obtained as a powder, and 2 to 2.5 moles of the esterifying agent are used per mole of the compound of formula (). In some cases, it is obtained as a powder or plastic. The hydrate obtained by this process, preferably as a powder, can be stored in storage tanks and transported without problems, so that further processing, for example to produce dyes, can be carried out in a timely and timely manner. It can be carried out locally without regard to esterification.

For further processing to produce dyes:
diazotization of the hydrate in Congo acidic aqueous solution. Depending on the case, depending on the amount of esterifying agent used in the esterification step, further addition of acid can be partially or completely omitted. Diazotization is carried out by known and customary methods. However, the hydrate is first dissolved neutrally in water with the addition of an acid binder, e.g. sodium carbonate or sodium bicarbonate, then a very small excess of sodium nitrite is added, and this solution is mixed with ice. It is advantageous to operate in a Congo acidic manner with an acid, for example hydrochloric acid. The diazonium salt thus formed is not isolated, but is added as a suspension with a coupling component of the formula H-K (where K has the meaning given above) and a suitable pH-value. After conditioning, it can be coupled to form the dye of formula () above.

The dye solution produced in this way has a relatively low content of sulfate derived from esterification, so
It is not necessary to precipitate the dye by salting out with sodium chloride or potassium chloride and then remove it; the weakly acidic to neutral dye solution can be conveniently evaporated to dryness or spray-dried as is. .

A highly tinting dye powder is thus obtained with excellent quality and purity in very good yields. This dye powder corresponds in its properties to the products produced by known methods, but generally β-
Degree of esterification of hydroxyethylsulfonyl group,
It is superior to the latter in terms of dye content of formula (), tinting power, water solubility and dye yield.

Since the dye has good solubility, the dye solution obtained can be used as is or, if necessary, after being further concentrated to a smaller volume for dyeing purposes.

Therefore, the present invention also relates to a simplified method for producing fiber-reactive azo dyes by using the product of formula () obtained by the esterification method according to the present invention, and its characteristics include: Ha〓
The compound is used as the diazo component, optionally neutrally dissolved in water, and diazotized in a conventional manner, followed by a reaction suitable for azo coupling.
After adjusting the pH value, the azo dye is coupled with a coupling component and the resulting azo dye is isolated by spray drying or evaporative concentration.

The examples given below are intended to illustrate the subject matter of the invention. Note that the relationship between parts by weight and parts by volume shown in the examples corresponds to the relationship between kg.

Example 1 (a) A commercially available dispersing summer machine (e.g. Werner & Pfleiderer, Stutt-gart-
4 as a dry powder in Feuerbach's product)
-Amino-3'-(β-hydroxyethylsulfonyl)-benzanilide 3200 parts by weight was charged,
Then, while operating the machine, add 65% oleum 1071.
The weight parts are added as a very thin jet within 45 minutes. The reaction mixture was heated for about 2 hours by adjusting the temperature with a heating or cooling jacket.
The mixture was left in an operating machine at a temperature of 80 to 100°C, then cooled to below 40°C, and then taken out from the machine.

The powder 4100 is thus slightly brownish-gray colored.
Parts by weight were obtained. This powder is 4-amino-
It was 92% for 3'-(β-sulfatoethylsulfonyl)-benzanilide (molecular weight 400). The degree of esterification was 97-98%.

(b) Add 2.0 parts by weight of the above hydrate to approx. 16 parts by volume of water are stirred into the mixture with 4 parts by weight of ice while simultaneously adding 65 parts by weight of sodium bicarbonate in portions. The pH value of the aqueous solution thus obtained was 5.0 to 5.5. The solution was filtered clear and evaporated to dryness under reduced pressure at 60-65°C. Thus, after grinding, in addition to 8% by weight of sodium sulfate, 2.1 parts by weight of a powder containing the pure compound in the form of its sodium salt were obtained.

Example 2 Commercial dispersion of 4-amino-3'-(β-hydroxyethylsulfonyl)- as a dry powder in a machine.
Charge 3200 parts by weight of benzanilide, and add 2111 g of 100% sulfuric acid within 40 minutes while the machine is running. The temperature remained below 100°C. The reaction mixture was mutually mixed for 2 hours in a machine operating at 80-100°C, then cooled to below 40°C and removed from the machine.

5080 parts by weight of powdered product were thus obtained.
This product is 75 for 4-amino-3'-(β-sulfatoethylsulfonyl)-benzanilide.
It was in weight%. The degree of esterification was 95%.

The hydrate obtained above can be worked up in the same manner as in Example 1b.

Example 3 Commercially available continuously operating machine rotating at 26 revolutions per minute (e.g. BUSS AG., Basel/Schweiz)
The 4-amino-
3'-(β-hydroxyethylsulfonyl)-benzanilide is introduced in an amount of 23.1 g/min and 65% oleum is introduced via a metering pump in an amount of 6.2 ml/min.
〓The Japanese machine is maintained at 100-110℃ using a heating jacket and a cooling jacket. The discharged product is 4-
It contained 82% by weight of amino-3'-(β-sulfatoethylsulfonyl)-benzanilide (molecular weight 400). The degree of esterification was 97%.

The hydrate thus obtained can be worked up analogously to Example 1b.

Examples 4 to 6 Working in the same manner as described in Examples 1, 2 or 3, the starting compounds listed in Examples 4 to 6 below give the following Tables with exactly the same high purity, high degree of esterification and high yield. The corresponding sulfuric acid half ester of the given formula (final product) was obtained: Example 7 87 parts by weight of the hydrate produced in Example 1a was added to 800 parts by weight of water.
PH6.5 with addition of sodium carbonate solution in volume parts
Dissolve at ~7 and then add 44.0 parts by volume of 5N sodium nitrite solution. The solution thus prepared is poured, with stirring, into a mixture of 400 parts by weight of ice and 60 parts by volume of 31% hydrochloric acid. After stirring for 1 hour, excess nitrite is decomposed with 2 parts by weight of amidosulfonic acid. Next, 136.3 parts by weight of 53% 1-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid was added, and crystalline sodium acetate was added to the reaction solution.
20 parts by weight and additionally 30 parts by weight of sodium carbonate
Raise the PH-value to 5 within minutes. After the coupling is completed, the resulting dye solution is treated with 20 parts by weight of diatomaceous earth to make it clear and concentrated by evaporation at 60°C.

By grinding the residue the following formula 280 parts by weight of a dark red powder were obtained, which was 55% by weight of the dye.

This dyestuff is a bright deep bluish red with good light fastness and very good wet fastness in the known conventional dyeing processes for reactive dyes on cellulosic fiber materials, e.g. cotton, in the presence of alkaline-acting agents. It produces dyeing and printing.

Example 8 In Example 7, an equimolar amount of 1-(4'-sulfophenyl)-3-carboxy-
Substituting pyrazolone-(5) and otherwise working as described in Example 7 gives the following formula in the free acid form: A yellow dye corresponding to is obtained. This product gives deep yellow dyeings and prints on cotton with excellent light and wet fastness properties by the known dyeing processes customary for reactive dyes.

Examples 7a and 8a The dyes described in Examples 7 and 8 above can also be prepared using the sulfuric acid half-esters synthesized according to Examples 2 and 3 in a similar or analogous manner.

Examples 4a-6a The sulfuric acid half ester-compounds prepared according to the invention which act as diazo components in Examples 7 and 8 or 7a and 8a are prepared according to the invention as described in Examples 4, 5 or 6. Replacement by equimolar amounts of the sulfuric acid half ester obtained gives the corresponding fiber-reactive azo dye. By dyeing and printing processes known for reactive dyes, this dyestuff produces similarly intense dyeings and prints on cellulose fiber materials, such as cotton, which also have good light and wet fastness properties.

Claims (1)

[Claims] Linear formula () Esterifying a compound represented by the formula "In the formula, the β-hydroxyethylsulfonyl group is present at the 3'- or 4'-position of the anilide group, and the amino group is present at the 3- or 4-position of the benzoyl group." Then, the following formula () A compound represented by the formula "In the formula, the β-sulfatoethylsulfonyl group is present at the 3'- or 4'-position of the anilide group, and the amino group is present at the 3- or 4-position of the benzoyl group." During production, the reaction
92 to 100, which is 1 to 2.5 times the molar amount of SO ₃
% sulfuric acid, sulfur trioxide, or sulfur trioxide-containing sulfuric acid in a machine that operates with a sulfuric action. 2. In the method described in claim 1,
A method comprising performing the esterification using an esterifying agent in an amount of 1.1 to 1.5 times the molar amount of SO ₃ . 3. A method according to claim 1 or 2, comprising using about 65% oleum as the esterifying agent. 4. In the method described in any one of claims 1 to 3, the reaction is carried out at 70 to 110°C.
How to be better than what you do. 5. A method according to any one of claims 1 to 4, which comprises carrying out the reaction in a softener that operates continuously. 6 In the method described in any one of claims 1 to 5, the following formula The compound shown by is esterified to form the following formula A method consisting of making a compound represented by: